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CN104934595B - Prepare the nickel cobalt aluminium precursor material being distributed with aluminium element gradient and the method for positive electrode - Google Patents

Prepare the nickel cobalt aluminium precursor material being distributed with aluminium element gradient and the method for positive electrode Download PDF

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CN104934595B
CN104934595B CN201510233112.6A CN201510233112A CN104934595B CN 104934595 B CN104934595 B CN 104934595B CN 201510233112 A CN201510233112 A CN 201510233112A CN 104934595 B CN104934595 B CN 104934595B
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aluminium
solution
nickel
complexing agent
cobalt
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CN104934595A (en
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吴层
谭潮溥
严亮
黄殿华
陈瑞祥
张郑
袁昌杰
骆宏钧
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GUANGZHOU LIBODE NEW MATERIAL Co Ltd
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GUANGZHOU LIBODE NEW MATERIAL Co Ltd
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Priority to CN201510233112.6A priority Critical patent/CN104934595B/en
Publication of CN104934595A publication Critical patent/CN104934595A/en
Priority to PCT/CN2016/081350 priority patent/WO2016180288A1/en
Priority to PL16792138T priority patent/PL3297072T3/en
Priority to US15/538,131 priority patent/US10329162B2/en
Priority to JP2017548519A priority patent/JP6395951B2/en
Priority to EP16792138.6A priority patent/EP3297072B1/en
Priority to KR1020177019081A priority patent/KR101952210B1/en
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    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
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    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The present invention relates to the method for preparing the nickel cobalt aluminium precursor material being distributed with aluminium element gradient and positive electrode.Precursor material prepared by the method for the present invention and the positive electrode based on the presoma are distributed spherical or spherical, the even particle size distribution changed in gradient for aluminium element.Synthesized material tap density is high, good processability insensitive to ambient carbon dioxide and moisture, and specific capacity is high, and stability characteristic (quality) is good.

Description

Nickel cobalt aluminium precursor material and positive electrode of the preparation with the distribution of aluminium element gradient Method
Technical field
Field is manufactured the present invention relates to lithium ion battery, the nickel cobalt aluminium being distributed more particularly to preparation with aluminium element gradient The method of precursor material and positive electrode.
Background technology
At present, lithium ion battery is had been widely used in various mobile electronic products and field of power tools, and just Pole material is that energy density, security are improved in lithium ion battery and the key of cost is reduced.Further improve the work(of material Rate density, energy density and improvement security performance are the developing direction of current anode material for lithium-ion batteries.
In LiCoO2Many replacement candidates materials in, LiNiO2Because its high power capacity, low cost, of low pollution and by people Concern；And LiNi1-xCoxO2Except with LiNiO2Outside height ratio capacity, the advantage of low cost, also with preferable cyclicity Can, LiNi1-xCoxO2190mAh/g specific capacity can have been given play to, but the stability of nickel cobalt binary material is still reached to less than existing rank The section requirement of 3C (household electrical appliances, computer, communication) electronic product and electrokinetic cell to material.
Bulk phase-doped and Surface coating is to improve the main method of nickel based material stability.Using nickel cobalt aluminum as representative Mix aluminum, LiNi1-x-yCoxAlyO2It is used as LiNiO2、LiCoO2And LiAlO2The isomorphism solid solution of three, has simultaneously High for energy density, heat endurance is good, the advantages of inexpensive environmentally friendly, has become the high-end storage in 3C fields and electrokinetic cell field Can material.But, due to the thermodynamic phase of nickelic, cause NCA (nickel cobalt aluminic acid lithium material) synthesis difficult, nickelous Ion is difficult to be oxidized to trivalent, it is necessary to could aoxidize under pure oxygen atmosphere completely.Further, since NCA water imbibitions are strong, in the presence of Reaction in formula, battery production needs normally to produce in the following condition of 10% humidity.Because NCA easily releases O2, CO2Deng, The easy inflatable of battery, is produced preferably with 18650 type cylindrical batteries.
LiNi1-x-yCoxAlyO2+H2O→Ni1-x-yCoxAlyO+LiOH+O2
LiOH+CO2→Li2CO3
Li2CO3+HF→LiF+CO2
In view of the architectural characteristic of the material in itself causes the condition of the stable NCA materials of preparation structure and nickel cobalt aluminium lithium battery It is very harsh.At present, the nickel cobalt aluminium lithium anode material of domestic production still has in charge and discharge process that capacity attenuation is very fast, multiplying power Performance is bad and the defect such as storge quality extreme difference.Therefore, in order to cater to gentle production technology, the superior nickel cobalt aluminium of processability Material, it is necessary to develop new nickel cobalt aluminium presoma.
In the preparation process of nickel cobalt lithium aluminate cathode material, because being limited by calcinating system, Al3+Ion~ It is difficult the method for forming solid solution with Ni-Co and seldom being sintered with independent nickel, cobalt, aluminum feedstock solid phase mixing at 750 DEG C.It is general at present All over thinking Ni1-x-yCoxAly(OH)2It is the optimal presoma for preparing high-performance nickel cobalt aluminium.Coprecipitation is to prepare LiNiCoAlO2 And its one kind of surface modification is simply, practical method.Ni, Co and Al co-precipitation, it is important to overcome Al3+Facile hydrolysis individually sinks Form sediment, the difficult presoma with nickel cobalt element formation single structure, it is impossible to form high density spherical nickel-cobalt aluminum.For Al3+The Yishui River Solution problem, patent CN103094546A and CN103553152A are proposed using the complex solution for individually preparing aluminium as silicon source, are used Cocurrent adding material mode and nickel cobalt salting liquid, sodium hydroxide solution and ammonia solution are by controlling crystallization to prepare the side of spherical nickel-cobalt aluminium Method.But there are the following problems for this method：1st, substantial amounts of sulfate ion is often remained in the nickel cobalt aluminium presoma prepared to be difficult Washing removing；2nd, CN103553152A 5%wt~15%wt sodium hydroxide solution ripenings are conducive to the removing of sulphur, still The loss of surface aluminium element is frequently can lead in washing process, cause prepare material surface lack aluminium and to the storage of positive electrode Sustainability energy, processing characteristics and electrochemical cycle stability are unfavorable.Improve aluminium doping can improve material cyclical stability, Security performance and processing characteristics and storge quality, but the introducing of substantial amounts of light metal alloy aluminium can cause material real density itself Reduction, cause the reduction of material volume energy density, and the introducing for not having electroactive Al elements necessarily causes material sheet The reduction of body energy density.So, high-energy-density is prepared in the case of relatively low Al dopings, high stability, excellent Storge quality and processing characteristics become a study hotspot.
South Korea Han Yang University Yang-Kook Sun just have developed new gradient lithium ion battery material early in 2008 Material, the kernel of the material is the higher nickel-cobalt-manganese ternary material of nickel content, outer roll cover for nickel content is gradually reduced and manganese with The nickel cobalt manganese material that cobalt content gradually rises.This special positive electrode show high-energy-density, the long-life and very well Security performance.Also there is the change of many documents and patent report doped chemical (Ni, Co, Mn, Mg, Al, Ti, Zr etc.) gradient the country The preparation method of the anode material for lithium-ion batteries of change.Wherein CN102214819 A, CN103078109 A and CN The hydroxide precursor that coprecipitation prepares the distribution of Al graded elementals is contained in the patents of invention such as 103715424 A.But It is that its method is that aluminum salt solution is gradually added into mixing nickel cobalt mixing salt solution to control aluminium in nickel cobalt aluminium mixing salt solution dense Degree gradually changes and prepares the hydroxide precursor with aluminium element graded.In ammonia complexing system used in it, Al3+It is several Discord ammonia complexing, Al3+Hydrolysis is easy to independently form colloid and do not reach Al3+Ladder of the element in nickel cobalt manganese hydroxide Degree doping, is unfavorable for preparing high-density spherical gradient and mixes aluminium presoma.
The content of the invention
The present invention provides a kind of use coprecipitation and prepares the method for ball-shape nickel hydroxide cobalt aluminium precursor material, and is based on The preparation method of the terraced aluminium profiles lithium ion battery lithium nickel cobalt alumina positive electrode of this method, to overcome and avoid prior art Shortcoming and defect is there is provided one kind is simple and easy to apply, and condition is easily controllable, can synthesize with excellent chemical property, superior The preparation method of the terraced aluminium profiles lithium ion battery lithium nickel cobalt alumina positive electrode of processing characteristics and storge quality.
Ball-shape nickel hydroxide cobalt aluminium precursor material is prepared using coprecipitation there is provided one kind according to the first aspect of the invention Method, the described method comprises the following steps:
A) prepare the nickel cobalt saline solution of nickel salt and cobalt salt mixing, the solution containing complexing agent I, contain the molten of complexing agent II Liquid and sodium hydroxide solution, and aluminium salt and complexing agent I are hybridly prepared into complex solution containing aluminium；
B) the bottom liquid containing the complexing agent II is previously added in a kettle.；
C) by the nickel cobalt saline solution, the solution containing complexing agent I, the solution containing complexing agent II, institute State complex solution containing aluminium and the sodium hydroxide solution add precipitation reaction in the reactor being stirred continuously obtain it is described before Material is driven, wherein the nickel cobalt saline solution, the solution containing complexing agent II and the sodium hydroxide solution are each with perseverance In constant current speed stream plus the addition reactor, the complex solution containing aluminium and the solution containing complexing agent I are in the following manner Add：By the complex solution containing aluminium with constant flow rate stream add described in fixed volume in the solution containing complexing agent I with The solution mixing containing complexing agent I, while by the mixing of the complex solution containing aluminium and the solution containing complexing agent I Solution adds the reactor with constant flow rate stream, so that aluminum concentration gradually increases in the mixed solution.
According to an embodiment of the present invention, nickel salt described in methods described is nickel sulfate, nickel chloride, nickel acetate and nitric acid One or more in nickel.
According to an embodiment of the present invention, cobalt salt described in methods described is cobaltous sulfate, cobalt chloride, cobalt acetate and nitric acid One or more in cobalt.
According to an embodiment of the present invention, the complexing agent I described in methods described is triethanolamine, ammonium fluoride, lemon One or more in acid, oxalic acid, sodium ethylene diamine tetracetate and sodium hydroxide.
According to an embodiment of the present invention, the complexing agent II described in methods described is ammoniacal liquor, triethanolamine, fluorination One or more in ammonium, citric acid, oxalic acid, sodium ethylene diamine tetracetate.
According to an embodiment of the present invention, the aluminium salt described in methods described is in aluminum nitrate, aluminum sulfate or aluminum acetate One or more.
According to an embodiment of the present invention, in nickel cobalt saline solution described in methods described nickel salt and cobalt salt mol ratio For 1-19, such as in described nickel cobalt saline solution the mol ratio of nickel salt and cobalt salt can for 1,2,3,4,5,6,7,8,9,10,11, 12nd, 13,14,15,16,17,18 or 19.
According to an embodiment of the present invention, in nickel cobalt saline solution described in methods described nickel salt and cobalt salt total concentration For 0.2~2.5mol/L, such as in described nickel cobalt saline solution the total concentration of nickel salt and cobalt salt can for 0.2mol/L, 0.4mol/L、0.6mol/L、0.8mol/L、1.0mol/L、1.2mol/L、1.4mol/L、1.6mol/L、1.8mol/L、 2.0mol/L, 2.2mol/L or 2.5mol/L.
According to an embodiment of the present invention, the concentration of sodium hydroxide solution described in methods described is 2~10mol/L, The concentration of such as described sodium hydroxide solution can for 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L or 10mol/L.
According to an embodiment of the present invention, aluminium element and the complexing agent in complex solution containing aluminium described in methods described I mol ratio is 1:0.01~20.0, such as aluminium element and the complexing agent I mol ratio can be with described complex solution containing aluminium For 1:0.01、1:0.05、1:0.1、1:0.2、1:0.3、1:0.3、1:0.4、1:0.5、1:0.6、1:0.7、1:0.8、1:0.9、 1:1.0、1:1.5、1:2.0、1:2.5、1:3.0、1:3.5、1:4.0、1:4.5、1:5.0、1:5.5、1:6.0、1:6.5、1: 7.0、1:7.5、1:8.0、1:8.5、1:9.0、1:10.0、1:11.0、1:12.0、1:13.0、1:14.0、1:15.0、1:16.0、 1:17.0、1:18.0、1:19.0 or 20.0.
According to an embodiment of the present invention, the complexing agent II of bottom liquid described in methods described concentration is 0.3~2mol/ L, such as described bottom liquid complexing agent II concentration can for 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L、0.8mol/L、0.9mol/L、1.0mol/L、1.1mol/L、1.2mol/L、1.3mol/L、1.4mol/L、 1.5mol/L, 1.6mol/L, 1.7mol/L, 1.8mol/L, 1.9mol/L or 2.0mol/L.
According to an embodiment of the present invention, the pH at bottom liquid described in methods described is 10~12, such as described bottom liquid PH can be 10,10.2,10.4,10.6,10.8,11,11.2,11.4,11.6,11.8 or 12.
According to an embodiment of the present invention, nickel cobalt saline solution described in methods described, described contain complexing agent II's The velocity ratio that solution, the sodium hydroxide solution and the mixed solution stream add the reactor is 1:(0.05~50): (0.1~10):(0.01~100).
According to an embodiment of the present invention, the stream of complex solution containing aluminium described in methods described adds the institute of fixed volume It is 0.1mL/min~2000mL/min to state the flow velocity in the solution containing complexing agent I.
According to an embodiment of the present invention, the mixing speed described in methods described in reactor be 50~1000 turns/ Minute.
According to an embodiment of the present invention, the reaction temperature in step c) described in methods described is 20~80 DEG C.
According to an embodiment of the present invention, the reaction time in step c) described in methods described is 5 to 100 hours.
There is provided a kind of system of terraced aluminium profiles lithium ion battery lithium nickel cobalt alumina positive electrode according to the second aspect of the invention Preparation Method, methods described includes：
1) ball-shape nickel hydroxide cobalt aluminium precursor material is prepared using the method as described in first aspect；
2) by step 1) obtain the precursor material washing, filtering and dry；
3) after the precursor material is uniformly mixed with lithium hydroxide, it is placed in oxygen atmosphere stove and calcines, be cooled to room temperature After obtain the terraced aluminium profiles lithium ion battery composite cathode material.
According to an embodiment of the present invention, step 2 described in methods described) include：By the precursor material with 20~ 80 DEG C, 10~60min of sodium chloride solution stirring and washing that concentration is 3~30wt%；B) it is clear using 20~80 DEG C of deionized water Wash precipitation for several times, be less than 10 to final ph；C) wet feed after cleaning is placed in dry 6~60h at 60~150 DEG C.
According to an embodiment of the present invention, step 3 described in methods described) include：By forerunner's material after cleaning-drying Material is uniformly mixed with lithium hydroxide, and 10~30h is calcined in 650~850 DEG C in oxygen atmosphere stove, is cooled to after room temperature and is obtained ladder Aluminium profiles lithium nickel cobalt alumina positive electrode.
The present invention is directed to Al3+Facile hydrolysis problem, it is proposed that individually to prepare the complex solution of aluminium as silicon source, silicon source solution by Gradually adding in intermediate solution (solution i.e. containing complexing agent I) causes the concentration of aluminium in mixed solution gradually to increase, by aluminium Concentration gradually answer in kettle and connect by increased mixed solution, nickel cobalt salting liquid, sodium hydroxide solution and enveloping agent solution cocurrent addition side Continuous reaction, so that aluminium element has gradient distribution from the centre of sphere to sphere in presoma.Spherical nickel-cobalt aluminium prepared by this method In material, the concentration of doping aluminium element is increased continuously from core to sphere, and surface aluminium content even can reach 100%.It is such The LiNi that presoma is prepared1-x-yCoxAlyO2Adulterated al concentration of element is increased continuously from core to sphere, and surface aluminium content is even 100% can be reached, diffusion of the lithium ion inside material body is not only improved, material is also fundamentally solved and exists Stability in air and in electrolyte, and can reduce and mix aluminum amount to improve the energy density of material.Using the present invention Method be prepared for a series of Ni-based gradient and mix aluminium composite material：LiNi0.815Co0.15Al0.035O2、 LiNi0.85Co0.10Al0.05O2And LiNi0.87Co0.10Al0.03O2Etc., prepared material shows high-energy-density, height Security and stability and superior processing characteristics.
Therefore, the method that the use coprecipitation that the present invention is provided prepares ball-shape nickel hydroxide cobalt aluminium precursor material, and The preparation method of terraced aluminium profiles lithium ion battery lithium nickel cobalt alumina positive electrode based on this method has multiple advantageous effects： (1) the gradient type ball-shape nickel hydroxide cobalt aluminium precursor material and positive electrode prepared using the method for the present invention, the concentration of aluminium Gradually increase from core to particle surface by radial direction, it is maximum in most surface concentration, 100% may be up to；(2) method energy of the invention Enough by strict control system condition, realize by origin of the ball-shape nickel hydroxide cobalt alumina particles centre of sphere to the uniform of surface aluminium element The preparation of increased presoma；(3) use the present invention method prepare gradient type ball-shape nickel hydroxide cobalt aluminium precursor material with And positive electrode, humidity resistance significantly improves, and the decomposition of nickelic is prevented effectively from, to humidity sensitive in the preparation and application of material Property is all substantially reduced, and is conducive to the manufacture of NCA materials and associated batteries；(4) compared with the conventional method, some in the present invention NaCl desulfurization washing steps are also add in embodiment, improve harmful while the loss of effective element in reducing presoma The removing of impurity, beneficial to the lithium nickel cobalt lithium aluminate cathode material for preparing high stability；(5) nickel cobalt prepared by this method Aluminic acid anode material of lithium battery, with stable electrochemical property, energy density big, good rate capability, safe, temperature, wet The features such as sensitiveness is low, processing characteristics is excellent is spent, the power electric needed for electronic product and electric automobile can be met for preparation Pond；(6) by controlling sintering process, the gradient type nickel cobalt lithium aluminate cathode material with high stability surface can be built, because This, the product purity of synthesis is high, and complete crystallization, processing characteristics is excellent, and chemical property is good；(7) method of the invention is simply easy OK, condition is easily controllable, green high-efficient.
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention, And can be practiced according to the content of specification, and in order to allow above and other objects of the present invention, feature and advantage can Become apparent, below especially exemplified by the embodiment of the present invention.
Brief description of the drawings
By reading the detailed description of hereafter preferred embodiment, various other advantages and benefit is common for this area Technical staff will be clear understanding.Accompanying drawing is only used for showing the purpose of preferred embodiment, and is not considered as to the present invention Limitation.In the accompanying drawings：
Fig. 1 is the schematic diagram of each feedstock mode in synthetic method of the invention.
Fig. 2 schemes for the presoma SEM prepared in embodiment 1.
Fig. 3 is the XRD comparison diagrams of terraced aluminium presoma and common co-precipitation presoma in embodiment 1.
Fig. 4 is the cycle performance curve of the positive electrode prepared in embodiment 1.
Fig. 5 is the SEM figures of the presoma prepared in embodiment 2.
Fig. 6 is the positive electrode prepared in embodiment 2 and charging and discharging curve (6a, 0.2C and the 1C multiplying power of common NCA materials Under) comparison diagram and cycle performance curve (6b) comparison diagram.
Embodiment
The illustrative embodiments of the disclosure are described in more detail below.Although hereinafter showing the example of the disclosure Property embodiment, it being understood, however, that may be realized in various forms the disclosure without should be by embodiments set forth herein institute Limitation.Conversely it is able to be best understood from the disclosure there is provided these embodiments, and can be by the scope of the present disclosure Complete conveys to those skilled in the art.Although it should be appreciated that those skilled in the art are not it is contemplated that in this theory It is expressly recited or records in bright book but realizes the present invention and each in present invention spirit, principle and scope The method of kind, component and content.All examples and conditional language quoted from this specification are all in order at what is illustrated and instruct Purpose, to help reader to understand principle and concept that inventor contributes to prior art, and should be understood that not limit The example and condition specifically quoted from these.In addition, in order to illustrate more clearly of, eliminate for known method, component and The detailed description of content, not obscure description of the invention.It should be understood that unless stated otherwise, each embodiment described herein In feature can be combined with each other.
Embodiment 1：
It is 2mol/L and Ni to prepare Ni+Co ion concentrations:Co=81.5:15 nickel cobalt saline solution 45L, mass concentration Ammonia spirit (solution of the II containing complexing agent) 20L for 14mol/L of 32% sodium hydroxide solution 30L, concentration, aluminium element content For 1mol/L sodium aluminate solution (aluminium and complex solution hydroxy) (aluminium complex solution) 3.26L, pH=12 hydroxide Sodium solution 41.74L (solution of the I containing complexing agent)；
40L ammoniacal liquor is previously added in 150L reactors, temperature is 50 DEG C, (NH3·H2O+NH4 +) concentration be 1mol/ L, pH are 11.50 ± 0.02 aqueous solution.Wherein, pH value is detected by pH meter, (NH3·H2O+NH4 +) concentration is by chemical titration Detect and accelerate slowly to adjust its concentration with concentrated ammonia liquor stream；
By the nickel cobalt saline solution (20ml/min), 30% sodium hydroxide solution (10 ± 2mL/min) and 14mol/L Ammonia spirit (4 ± 1mL/min) stream plus add in reactor, and sodium aluminate solution is first with 1.45ml/min flow velocity stream Plus add in the lasting stirring stainless steel equipped with volume for the 41.74L I containing complexing agent solution, while will be mixed molten Liquid is added in reactor (referring to Fig. 1) with 20ml/min flow velocity stream, and the reaction temperature in reactor is 50 DEG C；
Wherein specifically, after charging starts, because the liquor capacity of the I containing complexing agent in stainless steel is constantly reduced, and it is inclined Sodium aluminate solution is continuously added, the aluminium element concentration more and more higher in stainless steel, so that after the mixing fed into reactor Solution in aluminium element concentration also more and more higher, the aluminium element concentration that precipitation particle surface is touched also increases, finally Obtain the terraced aluminium profiles nickel cobalt aluminum hydroxide precursor material along the aluminium element gradient distribution of precipitation particle radial direction interface.
During strict control complexing agent concentration, pH value and size distribution, nickel cobalt saline solution stops reacting after feed. Slurry is after 30min is aged, filtrated stock, and with 60 DEG C, 10% sodium chloride solution stirring and washing 30min, slurry passes through Washing, filtering, dry after obtain surface aluminum concentration be 30at% Ni0.815Co0.15Al0.035(OH)2Presoma (its SEM figure ginsengs See Fig. 2), from SEM it can be seen from the figure thats, presoma pattern is spherical or spherical, and size distribution is concentrated.Should Ni0.815Co0.15Al0.035(OH)2With the lithium hydroxide for measuring ratio is uniform mix after, be placed in oxygen atmosphere stove 750 DEG C of calcining 12h It is cooled to room temperature and obtains positive electrode LiNi0.815Co0.15Al0.035O2, XRD detects that the material has single α-NaFeO3Structure (referring to Fig. 3).Discharge capacity is 198mAh/g to the positive electrode first under 2.8~4.3 voltage window discharge and recharge 0.1C, under 1C Specific discharge capacity is maintained at 174mAh/g, circulates 300 weeks capability retention ＞ 82% (shown in Fig. 4).
Embodiment 2
It is 2mol/L and Ni to prepare Ni+Co ion concentrations:Co=80:15 nickel cobalt saline solution 45L, mass concentration 30% Sodium hydroxide solution 30L, concentration be 1mol/L EDTA (sodium ethylene diamine tetracetate) solution (solution of the II containing complexing agent) 10L, aluminium element content are 2mol/L Al-EDTA solution (aluminium complex solution) 2.37L, and concentration is molten for 0.02mol/L EDTA Liquid (solution of the I containing complexing agent) 42.63L；
40LEDTA solution is previously added in 150L reactors, temperature is 50 DEG C, EDTA concentration is 0.05mol/L, pH For 11.20 ± 0.02 aqueous solution.Wherein, pH value is detected by pH meter, and EDTA concentration is detected by chemical titration and used containing complexing Agent II solution stream is accelerated slowly to adjust its concentration；
By the nickel cobalt saline solution (20ml/min), 30% sodium hydroxide solution (10 ± 2mL/min) and 1mol/L EDTA solution (3 ± 1mL/min) stream plus add in reactor, and Al-EDTA complex solutions are first with 1.05ml/min stream Speed stream is added in the lasting stirring stainless steel equipped with volume for the 42.36L I containing complexing agent solution, while after mixing Solution added with 20ml/min flow velocity stream in reactor (referring to Fig. 1), the reaction temperature in reactor is 50 DEG C, stirring Speed is 400r/min；
During strict control complexing agent concentration, pH value and size distribution, nickel cobalt saline solution stops reacting after feed. Slurry is after 30min is aged, filtrated stock, and with 60 DEG C, 10% sodium chloride solution stirring and washing 30min, slurry passes through Washing, filtering, dry after obtain surface aluminum concentration be 50at% Ni0.80Co0.15Al0.05(OH)2Presoma (its SEM figure referring to Fig. 5), from SEM it can be seen from the figure thats, presoma pattern is spherical or spherical, and size distribution is concentrated.By Ni0.80Co0.15Al0.05 (OH)2With the lithium hydroxide for measuring ratio is uniform mix after, be placed in oxygen atmosphere stove 750 DEG C of calcining 12h and be cooled to room temperature acquisition Positive electrode LiNi0.8Co0.15Al0.05O2.The positive electrode discharges first under 2.8~4.3 voltage window discharge and recharge 0.2C Capacity is that specific discharge capacity is maintained at 178mAh/g under 188mAh/g, 1C, cycle performance be substantially better than common NCA materials (referring to Fig. 6).
It should be noted that the present invention will be described rather than limits the invention for above-mentioned embodiment, and ability Field technique personnel can design various alternate embodiments in the case of without departing from scope of the following claims.Affiliated skill The technical staff in art field it will be clearly understood that any improvement in the present invention, equivalence replacement to component selected by the present invention and The increase of helper component, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and being open.

Claims (20)

1. a kind of method that use coprecipitation prepares ball-shape nickel hydroxide cobalt aluminium precursor material, it is characterised in that methods described Comprise the following steps:
A) prepare nickel salt and cobalt salt mixing nickel cobalt saline solution, the solution containing complexing agent I, the solution containing complexing agent II and Sodium hydroxide solution, and aluminium salt and complexing agent I are hybridly prepared into complex solution containing aluminium；
B) the bottom liquid containing the complexing agent II is previously added in a kettle.；
C) by the nickel cobalt saline solution, the solution containing complexing agent I, the solution containing complexing agent II, described contain Aluminium complex solution and the sodium hydroxide solution add precipitation reaction in the reactor being stirred continuously and obtain forerunner's material Material, wherein the nickel cobalt saline solution, the solution containing complexing agent II and the sodium hydroxide solution are each with steady flow In speed stream plus the addition reactor, the complex solution containing aluminium and the solution containing complexing agent I are added in the following manner： The complex solution containing aluminium is added with constant flow rate stream and contained in the solution containing complexing agent I described in fixed volume with described The solution for having complexing agent I is mixed, at the same by the mixed solution of the complex solution containing aluminium and the solution containing complexing agent I with Constant flow rate stream adds the reactor, so that aluminum concentration gradually increases in the mixed solution.
2. according to the method described in claim 1, it is characterised in that：The nickel salt is nickel sulfate, nickel chloride, nickel acetate and nitric acid One or more in nickel.
3. according to the method described in claim 1, it is characterised in that：The cobalt salt is cobaltous sulfate, cobalt chloride, cobalt acetate and nitric acid One or more in cobalt.
4. according to the method described in claim 1, it is characterised in that：Described complexing agent I is triethanolamine, ammonium fluoride, lemon One or more in acid, oxalic acid, sodium ethylene diamine tetracetate and sodium hydroxide.
5. according to the method described in claim 1, it is characterised in that：Described complexing agent II is ammoniacal liquor, triethanolamine, fluorination One or more in ammonium, citric acid, oxalic acid, sodium ethylene diamine tetracetate.
6. according to the method described in claim 1, it is characterised in that：Described aluminium salt is in aluminum nitrate, aluminum sulfate or aluminum acetate One or more.
7. according to the method described in claim 1, it is characterised in that：The mol ratio of nickel salt and cobalt salt in the nickel cobalt saline solution For 1-19.
8. according to the method described in claim 1, it is characterised in that：The total concentration of nickel salt and cobalt salt in the nickel cobalt saline solution For 0.2~2.5mol/L.
9. according to the method described in claim 1, it is characterised in that：The concentration of the sodium hydroxide solution is 2~10mol/L.
10. according to the method described in claim 1, it is characterised in that：Aluminium element and the complexing in the complex solution containing aluminium Agent I mol ratio is 1:0.01~20.0.
11. according to the method described in claim 1, it is characterised in that：The concentration of the bottom liquid complexing agent II be 0.3~ 2mol/L。
12. according to the method described in claim 1, it is characterised in that：The pH of the bottom liquid is 10~12.
13. according to the method described in claim 1, it is characterised in that：The nickel cobalt saline solution, described contain complexing agent II's The velocity ratio that solution, the sodium hydroxide solution and the mixed solution stream add the reactor is 1:(0.05~50): (0.1~10):(0.01~100).
14. according to the method described in claim 1, it is characterised in that：The stream of complex solution containing aluminium adds fixed volume Flow velocity in the solution containing complexing agent I is 0.1mL/min~2000mL/min.
15. according to the method described in claim 1, it is characterised in that：Mixing speed in the reactor for 50~1000 turns/ Minute.
16. according to the method described in claim 1, it is characterised in that：Reaction temperature in the step c) is 20~80 DEG C.
17. according to the method described in claim 1, it is characterised in that：Reaction time in the step c) is 5 to 100 hours.
18. a kind of preparation method of terraced aluminium profiles lithium ion battery lithium nickel cobalt alumina positive electrode, it is characterised in that methods described bag Include：
1) ball-shape nickel hydroxide cobalt aluminium precursor material is prepared using the method as described in any one in claim 1-17；
2) by step 1) obtain the precursor material washing, filtering and dry；
3) after the precursor material is uniformly mixed with lithium hydroxide, it is placed in oxygen atmosphere stove and calcines, be cooled to after room temperature and obtain Obtain the terraced aluminium profiles lithium ion battery composite cathode material.
19. the preparation method of terraced aluminium profiles lithium ion battery lithium nickel cobalt alumina positive electrode according to claim 18, it is special Levy and be：The step 2) include：The precursor material is stirred with 20~80 DEG C, concentration for 3~30wt% sodium chloride solution Mix 10~60min of cleaning；Using 20~80 DEG C of deionized water cleaning precipitations for several times, it is less than 10 to final ph；After cleaning Wet feed be placed at 60~150 DEG C dry 6~60h.
20. the preparation method of the terraced aluminium profiles lithium ion battery lithium nickel cobalt alumina positive electrode according to claim 18 or 19, It is characterized in that：The step 3) include：Precursor material after cleaning-drying is uniformly mixed with lithium hydroxide, in oxygen atmosphere 10~30h is calcined in 650~850 DEG C in stove, is cooled to after room temperature and obtains terraced aluminium profiles lithium nickel cobalt alumina positive electrode.
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